US4261791A - Two step method of cleaning silicon wafers - Google Patents

Two step method of cleaning silicon wafers Download PDF

Info

Publication number
US4261791A
US4261791A US06/078,795 US7879579A US4261791A US 4261791 A US4261791 A US 4261791A US 7879579 A US7879579 A US 7879579A US 4261791 A US4261791 A US 4261791A
Authority
US
United States
Prior art keywords
solution
wafers
film
volume
wafer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/078,795
Inventor
Stanley Shwartzman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RCA Corp
Original Assignee
RCA Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RCA Corp filed Critical RCA Corp
Priority to US06/078,795 priority Critical patent/US4261791A/en
Priority to SE8006355A priority patent/SE8006355L/en
Priority to IT24611/80A priority patent/IT1141041B/en
Priority to DE19803035020 priority patent/DE3035020A1/en
Priority to JP13366280A priority patent/JPS5655053A/en
Application granted granted Critical
Publication of US4261791A publication Critical patent/US4261791A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052—Wet cleaning only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S134/00—Cleaning and liquid contact with solids
    • Y10S134/902—Semiconductor wafer

Definitions

  • the invention relates to the field of cleaning semiconductor wafers and more particularly to the field of cleaning silicon semiconductor wafers.
  • Freshly sawn, lapped or ground silicon wafers are extremely dirty and must be cleaned, if subsequent electronic device fabrication processes are to be successful.
  • the components of the dirt on the wafers are spindle oil; handcream; silicon particles; silicon powder; cooling solution, including wetting agents; lapping and polishing grit; epoxy casting compounds; human fingerprints and possibly other materials. If this dirt is not removed from the wafers, subsequent processing steps are adversely affected.
  • the assignee's material preparation department utilized a swab test comprising dipping a cotton swab in methylene chloride and scrubbing it across the wafer.
  • the wafer was only considered clean if the swab looked clean following the scrubbing of the wafer.
  • Many wafers cleaned in the best prior art cleaners required recleaning because they failed the swab test after their initial cleaning. Recleaning increases production costs and reduces yields because of increased wafer breakage.
  • An improved wafer cleaning technique is needed which assures the production of clean wafers in an economical manner.
  • a single cleaning system for all wafers is highly desirable, as is one which does not leach the dopant from the heavily doped P-type wafers.
  • the wafers are treated with a film forming solution which reacts with the wafers and/or the dirt to form a film on the wafer surface.
  • the wafers are preferably then rinsed in deionized water and immersed in a film stripping solution which removes the film formed by the first solution and leaves the wafers clean.
  • Both the film forming solution and the film stripping solution may be formulated from separate aqueous source solutions comprising 49% HF by weight and 70% HNO 3 by weight, respectively.
  • the film forming solution preferably comprises 99.1% to 99.5% by volume of the HF source solution and 0.5% to 0.9% by volume of the HNO 3 source solution; with 99.3% and 0.7% being preferred, respectively.
  • the film stripping solution preferably comprises 1% to 5% by volume of the HF source solution and 99% to 95% by volume of the HNO 3 source solution. However, many other stripping solutions can be used if desired.
  • the wafers to be cleaned are preferably immersed in the film forming solution for about one minute at room temperature, then rinsed in deionized water and immersed in the preferred film stripping solution for approximately one minute at room temperature. After removal from the stripping solution, the wafers are preferably rinsed in deionized water and then dried.
  • a three part cleaning process work damaged, dirty or even clean silicon wafers to be cleaned are subjected to a three part cleaning process.
  • the wafers are inserted in an ultrasonic cleaner containing a cleaning solution such as Chemcrest 5 with a small quantity of Triton X-100 added to it.
  • Triton X-100 is a wetting agent sold by Rohm and Haas.
  • the wafers are rinsed in water for one minute.
  • This first cleaning step is not essential, but is used because it prolongs the life of the more expensive solutions used in the second and third steps by removing many particles and some dust from the surface of the wafer.
  • the still dirty wafers are immersed in a film forming bath which reacts with the wafers to form a film thereon.
  • the exact nature of the reaction is unknown at this time.
  • the reaction may be only with the wafer, with both the wafer and the dirt, or possibly just the dirt.
  • it is believed to involve some reaction with the wafer itself since the film will form even on a clean wafer.
  • the term "reacts with the wafers" is used to encompass whatever form the reaction in fact takes and the term dirt is used to encompass undesirable materials and objects on the surface of the wafer.
  • the film forming solution may be mixed from separate aqueous source solutions of 49% HF by weight and 70% HNO 3 by weight, respectively.
  • the film forming solution preferably comprises about 0.5% to 0.9% by volume of the nitric acid source solution and about 99.5% to 99.1% by volume of the HF source solution with a small quantity of a wetting agent such as Cold Water All or Triton X-100 added as a wetting agent.
  • a wetting agent such as Cold Water All or Triton X-100 added as a wetting agent.
  • the preferred composition for this film forming solution is 0.7% by volume of the HNO 3 source solution and 99.3% by volume of the HF source solution, with a minute quantity of Triton X-100 added. This solution is preferably held at a temperature of about 25° C.
  • a satisfactory film is formed on high resistivity "N" and "P" wafers after about fifteen seconds of immersion. About one minute of immersion is needed to form a satisfactory film on heavily doped P-type wafers. Immersion of the high resistivity wafers in the film forming solution for a full minute produces no detected adverse effects. Thus, although different wafer types can be cleaned using different durations of immersion in the film forming solution, it is preferred to always use a one minute immersion in the film former because of the resulting processing simplicity and the assurance that all wafer types will be thoroughly cleaned.
  • This step forms a film on the wafer surface.
  • This film normally appears to be a very dark stain and may be very nonuniform in color.
  • This film is of undetermined chemical composition, but is similar in appearance to the brown stains which have appeared in spots on wafers in the past as a result of improper quenching of etched wafers at the end of a device fabrication etching step.
  • the semiconductor industry has for many years sought to avoid forming these stains because of the additional processing steps needed to remove them. It is believed that upon removal of the wafer from this film forming solution the dirt which was adhering to the wafer has been loosened or removed by chemical reactions involving the film forming solution.
  • the wafers are next preferably rinsed for one minute in deionized water in order to conserve the solutions and maximize their useful life.
  • the wafers is inserted in a film stripping solution.
  • the film stripping solution preferably comprises 95% to 99% by volume of the HNO 3 source solution and 5% to 1% by volume of the HF source solution. This solution reacts with the film covered wafers to remove the film. This solution is preferably kept at a temperature of about 25° C. After one minute of immersion in this film stripping solution, the wafers are removed, rinsed in deionized water and dried. Following the completion of this step, the wafers are clean and hydrophobic.
  • composition of the film stripping solution is not critical. Any of a vast number of solutions will do the job, including a solution comprising 20 vol% HF and 80 vol% HNO 3 . However, if strong etchants (including 20% HF/80% HNO 3 ) are used, the one minute immersion time must be shortened if the removal of large quantities of silicon is to be prevented.
  • Wafers processed in accordance with the above preferred embodiment universally pass the swab test for wafer cleanliness.
  • the nitric acid source solution comprise 0.7% ⁇ 0.2% by volume of the mixture. It is preferred that the nitric acid content be between 0.6% and 0.8% and preferably 0.7% ⁇ 0.05%. A concentration of 0.7% is considered ideal. At this concentration, a very dark stain is formed on the silicon wafer. Too much nitric acid results in the removal of too much silicon. Too little nitric acid causes the film to form more slowly and can leave dirt on the wafers, thus making the cleaning process ineffective. Since HNO 3 is volatile, it may be necessary to add small quantities of HNO 3 to the bath periodically to maintain the HNO 3 concentration at its desired value.
  • the wafers With the prior art cleaning solutions which the assignee previously utilized, it was very important that the wafers be kept wet prior to cleaning because upon drying-out many of the contaminants on the wafer became much harder to remove. This is not necessary when the present cleaning technique is used. However, if desired, the wafers may be kept wet at least until after they have been removed from the film forming solution.
  • the wafer may be stored in that condition and only immersed in a stripping solution when the wafer is about to be processed further for the preparation of semiconductor devices therein.
  • Both the film forming and film stripping solutions are preferably maintained at temperatures between about 18° C. and about 37° C. during the cleaning process with a range of 30° C. to 36° C. preferred.
  • the lower limit of 18° C. is established when the preferred 0.7% nitric acid solution is used because an adequate film is not formed in one minute at temperatures below 18° C.
  • the upper limit of about 37° C. on the solutions' operating temperature is chosen in the interest of limiting the rate of material removal from the wafer surfaces. Higher temperatures may be used if the rate of material removal is considered unimportant or if a high rate is desired. When utilized in the preferred manner, this cleaning process does not change the surface contours of the wafer.
  • This cleaning process removes all contaminants such as spindle oil, handcream, silicon particles, silicon powder, sawing coolant, wetting agents, lapping and polishing grit, epoxy casting compounds, fingerprint and whatever other dirt is on the wafers. This is accomplished without significantly leaching highly doped P-type wafers and without other adverse effects.
  • the particular times of immersion in the film forming and the film stripping solutions are selected to encompass the worst case needs for the hardest to clean wafers. These times may be adjusted in accordance with the characteristics of the wafers being cleaned.
  • this cleaning process removes about 0.1 to 0.2 mils of material from each side of the wafer.
  • compositions may be utilized as the film stripping solution since the cleaning process is much less sensitive to the composition of the stripping solution than it is to the composition of the film forming solution.
  • the preferred solution compositions and solution operating temperatures are in part selected with an eye to forming the film in a reasonable time, minimizing the removal of material from the substrate and of maximizing solution useful life. If such considerations are not important, or if it is desired to remove additional material from the wafer surfaces, then other temperatures and solution compositions may be utilized.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

Silicon wafers are cleaned by first immersing them in a film forming solution which reacts with the dirty wafers to form a film on the wafers and then immersing the wafers in a film stripping solution which removes the film. For silicon wafers both the film forming solution and the film stripping solution may be formed from separate aqueous source solutions comprising 49% HF by weight and 70% HNO3 by weight, respectively. The film forming solution comprises 99.1% to 99.5% by volume the HF solution and 0.5% to 0.9% by volume the HNO3 solution. A small quantity of a wetting agent may be present in this solution. The stripping solution comprises 95% to 99% by volume of the HNO3 solution and 5% to 1% by volume of the HF solution. When utilized at room temperature the film forming solution forms a film on the wafers and the stripping solution removes the film with a minimum of attack on the silicon of the main wafer body. This silicon wafer cleaning method is successful with all silicon wafers independent of doping level.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to the field of cleaning semiconductor wafers and more particularly to the field of cleaning silicon semiconductor wafers.
2. Prior Art
Freshly sawn, lapped or ground silicon wafers are extremely dirty and must be cleaned, if subsequent electronic device fabrication processes are to be successful. Among the components of the dirt on the wafers are spindle oil; handcream; silicon particles; silicon powder; cooling solution, including wetting agents; lapping and polishing grit; epoxy casting compounds; human fingerprints and possibly other materials. If this dirt is not removed from the wafers, subsequent processing steps are adversely affected.
In attempting to find an adequate cleaning solution for cleaning all types of wafers, the assignee's materials preparation department evaluated more than 50 commercially available compositions. Most wafers can be cleaned in acid baths. However, heavily doped P-type wafers have required 20% hot KOH and even then do not come out really clean. Further, the hot KOH is reported to leach the dopant from the heavily doped P-type wafers. No single commercial cleaning composition was found which would adequately clean all wafers types and doping levels. Even the best materials for a given wafer type often left wafers dirty.
As a means of determining wafer cleanliness, the assignee's material preparation department utilized a swab test comprising dipping a cotton swab in methylene chloride and scrubbing it across the wafer. The wafer was only considered clean if the swab looked clean following the scrubbing of the wafer. Many wafers cleaned in the best prior art cleaners required recleaning because they failed the swab test after their initial cleaning. Recleaning increases production costs and reduces yields because of increased wafer breakage.
The best of the acidic commercial solutions was selected for use in cleaning all wafers except the heavily doped P-type wafers. This solution cleans approximately 4,000 wafers in 18 gallons of cleaning solution before the solution must be discarded. The wafers are immersed in this solution for seven seconds.
An improved wafer cleaning technique is needed which assures the production of clean wafers in an economical manner. A single cleaning system for all wafers is highly desirable, as is one which does not leach the dopant from the heavily doped P-type wafers.
SUMMARY OF THE INVENTION
The above problems of the prior art wafer cleaning solutions are overcome by the present invention through use of a two-step cleaning process. This process will clean all wafer types and does not significantly leach the dopant from heavily doped P-type wafers. This cleaning process is particularly useful with any work damaged surface, but is not restricted to work damaged surfaces.
First, the wafers are treated with a film forming solution which reacts with the wafers and/or the dirt to form a film on the wafer surface. The wafers are preferably then rinsed in deionized water and immersed in a film stripping solution which removes the film formed by the first solution and leaves the wafers clean. Both the film forming solution and the film stripping solution may be formulated from separate aqueous source solutions comprising 49% HF by weight and 70% HNO3 by weight, respectively. The film forming solution preferably comprises 99.1% to 99.5% by volume of the HF source solution and 0.5% to 0.9% by volume of the HNO3 source solution; with 99.3% and 0.7% being preferred, respectively. A small quantity of a wetting agent may be included in this film forming solution. The film stripping solution preferably comprises 1% to 5% by volume of the HF source solution and 99% to 95% by volume of the HNO3 source solution. However, many other stripping solutions can be used if desired.
The wafers to be cleaned are preferably immersed in the film forming solution for about one minute at room temperature, then rinsed in deionized water and immersed in the preferred film stripping solution for approximately one minute at room temperature. After removal from the stripping solution, the wafers are preferably rinsed in deionized water and then dried.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In accordance with the preferred embodiment of this invention, work damaged, dirty or even clean silicon wafers to be cleaned are subjected to a three part cleaning process. First, the wafers are inserted in an ultrasonic cleaner containing a cleaning solution such as Chemcrest 5 with a small quantity of Triton X-100 added to it. Triton X-100 is a wetting agent sold by Rohm and Haas. After a minute of ultrasonic cleaning, which removes large particles, the wafers are rinsed in water for one minute. This first cleaning step is not essential, but is used because it prolongs the life of the more expensive solutions used in the second and third steps by removing many particles and some dust from the surface of the wafer.
Second, the still dirty wafers are immersed in a film forming bath which reacts with the wafers to form a film thereon. The exact nature of the reaction is unknown at this time. Thus, the reaction may be only with the wafer, with both the wafer and the dirt, or possibly just the dirt. However, it is believed to involve some reaction with the wafer itself since the film will form even on a clean wafer. Thus, the term "reacts with the wafers" is used to encompass whatever form the reaction in fact takes and the term dirt is used to encompass undesirable materials and objects on the surface of the wafer.
The film forming solution may be mixed from separate aqueous source solutions of 49% HF by weight and 70% HNO3 by weight, respectively. The film forming solution preferably comprises about 0.5% to 0.9% by volume of the nitric acid source solution and about 99.5% to 99.1% by volume of the HF source solution with a small quantity of a wetting agent such as Cold Water All or Triton X-100 added as a wetting agent. The preferred composition for this film forming solution is 0.7% by volume of the HNO3 source solution and 99.3% by volume of the HF source solution, with a minute quantity of Triton X-100 added. This solution is preferably held at a temperature of about 25° C. A satisfactory film is formed on high resistivity "N" and "P" wafers after about fifteen seconds of immersion. About one minute of immersion is needed to form a satisfactory film on heavily doped P-type wafers. Immersion of the high resistivity wafers in the film forming solution for a full minute produces no detected adverse effects. Thus, although different wafer types can be cleaned using different durations of immersion in the film forming solution, it is preferred to always use a one minute immersion in the film former because of the resulting processing simplicity and the assurance that all wafer types will be thoroughly cleaned.
Although immersion of the wafers in the film forming solution is preferred, other treatment techniques such as dipping, spraying or spinning may be used if desired.
After one minute of immersion in this film forming solution, the wafers are removed. This step forms a film on the wafer surface. This film normally appears to be a very dark stain and may be very nonuniform in color. This film is of undetermined chemical composition, but is similar in appearance to the brown stains which have appeared in spots on wafers in the past as a result of improper quenching of etched wafers at the end of a device fabrication etching step. The semiconductor industry has for many years sought to avoid forming these stains because of the additional processing steps needed to remove them. It is believed that upon removal of the wafer from this film forming solution the dirt which was adhering to the wafer has been loosened or removed by chemical reactions involving the film forming solution. The wafers are next preferably rinsed for one minute in deionized water in order to conserve the solutions and maximize their useful life.
As the third step in the cleaning process, the wafers is inserted in a film stripping solution. The film stripping solution preferably comprises 95% to 99% by volume of the HNO3 source solution and 5% to 1% by volume of the HF source solution. This solution reacts with the film covered wafers to remove the film. This solution is preferably kept at a temperature of about 25° C. After one minute of immersion in this film stripping solution, the wafers are removed, rinsed in deionized water and dried. Following the completion of this step, the wafers are clean and hydrophobic.
The composition of the film stripping solution is not critical. Any of a vast number of solutions will do the job, including a solution comprising 20 vol% HF and 80 vol% HNO3. However, if strong etchants (including 20% HF/80% HNO3) are used, the one minute immersion time must be shortened if the removal of large quantities of silicon is to be prevented.
The ability of this system to function with the wafers held in each of the solutions for one minute makes it ideal for mechanized transfer systems, since the wafers can be indexed simultaneously at all stages of the cleaning. Further, the one minute immersion times make the insertion and removal times of the wafer holders a non-significant factor in the process. The prior art system where wafers could only remain in the cleaning tank for seven seconds was not amenable to mechanized operation and made insertion and removal times a significant portion of the process time.
Wafers processed in accordance with the above preferred embodiment, universally pass the swab test for wafer cleanliness.
It is desirable to control the nitric acid content of the film forming solution quite accurately. Although a broader composition range may be useful in some circumstances, it is preferred that the nitric acid source solution comprise 0.7%±0.2% by volume of the mixture. It is preferred that the nitric acid content be between 0.6% and 0.8% and preferably 0.7%±0.05%. A concentration of 0.7% is considered ideal. At this concentration, a very dark stain is formed on the silicon wafer. Too much nitric acid results in the removal of too much silicon. Too little nitric acid causes the film to form more slowly and can leave dirt on the wafers, thus making the cleaning process ineffective. Since HNO3 is volatile, it may be necessary to add small quantities of HNO3 to the bath periodically to maintain the HNO3 concentration at its desired value.
With the prior art cleaning solutions which the assignee previously utilized, it was very important that the wafers be kept wet prior to cleaning because upon drying-out many of the contaminants on the wafer became much harder to remove. This is not necessary when the present cleaning technique is used. However, if desired, the wafers may be kept wet at least until after they have been removed from the film forming solution.
If desired, once the film has been formed on the wafer, the wafer may be stored in that condition and only immersed in a stripping solution when the wafer is about to be processed further for the preparation of semiconductor devices therein.
Both the film forming and film stripping solutions are preferably maintained at temperatures between about 18° C. and about 37° C. during the cleaning process with a range of 30° C. to 36° C. preferred. The lower limit of 18° C. is established when the preferred 0.7% nitric acid solution is used because an adequate film is not formed in one minute at temperatures below 18° C. The upper limit of about 37° C. on the solutions' operating temperature is chosen in the interest of limiting the rate of material removal from the wafer surfaces. Higher temperatures may be used if the rate of material removal is considered unimportant or if a high rate is desired. When utilized in the preferred manner, this cleaning process does not change the surface contours of the wafer.
Both the film forming and the film stripping reactions are exothermic. Thus, if large quantities of wafers are treated, some cooling may be needed to keep the temperatures within the preferred temperature range.
With this system one 18 gallon charge of film forming solution and one 18 gallon charge of film stripping solution has been used to clean more than 12,000 three inch diameter silicon wafers when none of the wafers were heavily doped P-type. However, when heavily doped P-type wafers are cleaned along with wafers having other doping levels, the useful life of the solutions was found to be about 8,000-8,500 wafers per 18 gallon charge of each solution. With a 12,000 wafer capacity, this cleaning system is less expensive per wafer than the previous system. With an 8,000-8,500 wafer capacity, this system is slightly more expensive per wafer than the previous system. In either situation, this system is much more cost effective than the prior art system because it much more reliably produces truly clean wafers. This eliminates the problem of dirty wafers and the added costs of recleaning those wafers which were not clean.
This cleaning process removes all contaminants such as spindle oil, handcream, silicon particles, silicon powder, sawing coolant, wetting agents, lapping and polishing grit, epoxy casting compounds, fingerprint and whatever other dirt is on the wafers. This is accomplished without significantly leaching highly doped P-type wafers and without other adverse effects.
The particular times of immersion in the film forming and the film stripping solutions are selected to encompass the worst case needs for the hardest to clean wafers. These times may be adjusted in accordance with the characteristics of the wafers being cleaned.
When utilized in accordance with the preferred embodiment, this cleaning process removes about 0.1 to 0.2 mils of material from each side of the wafer.
Many different compositions may be utilized as the film stripping solution since the cleaning process is much less sensitive to the composition of the stripping solution than it is to the composition of the film forming solution.
The preferred solution compositions and solution operating temperatures are in part selected with an eye to forming the film in a reasonable time, minimizing the removal of material from the substrate and of maximizing solution useful life. If such considerations are not important, or if it is desired to remove additional material from the wafer surfaces, then other temperatures and solution compositions may be utilized.
An improved system for cleaning wafers has been described. Those skilled in the art will be able to vary the details of the preferred embodiments without departing from the scope of the invention as defined in the appended claims.

Claims (9)

What is claimed is:
1. A method of cleaning a dirty silicon semiconductor wafer comprising:
intentionally exposing the wafer to an environment which reacts with the wafer to form a dirt removing film on the wafer, said environment being a film forming solution initially comprising effectively:
99.1%-99.5% by volume of an aqueous source solution of 49% by weight HF; and
0.5%-0.9% by volume of an aqueous source solution of 70% by weight HNO3 ; and
subsequently removing said film in order to leave a clean wafer surface.
2. The method recited in claim 1 wherein:
said film forming solution includes a wetting agent.
3. The method recited in claim 1 wherein:
said film forming solution comprises effectively 0.7%±0.05% by volume of said HNO3 source solution.
4. The method recited in claim 1 wherein said removing step comprises:
treating said wafer with a film stripping solution initially comprising effectively:
80%-99% by volume of said source solution of HNO3 ; and
1%-20% by volume of said source solution of HF.
5. The method recited in claim 4 wherein said stripping solution initially comprises effectively:
95%-99% by volume of said source solution of HNO3 ; and
1%-5% by volume of said source solution of HF.
6. The method recited in claim 5 wherein said stripping solution initially comprises effectively:
substantially 95% by volume of said source solution of HNO3 ; and
substantially 5% by volume of said source solution of HF.
7. A method of cleaning a dirty silicon semiconductor wafer comprising:
intentionally exposing the wafer to an environment which reacts with the wafer to form a dirt removing film on the wafer, said environment being a film forming solution initially comprising effectively:
99.1%-99.5% by volume of an aqueous source solution of 49% by weight HF; and
0.5%-0.9% by volume of an aqueous source solution by 70% by weight HNO3 ; and
subsequently removing said film in order to leave a clean wafer surface, said removing being accomplished by treating said wafer with a film stripping solution initially comprising effectively:
95%-99% by volume of said source solution of HNO3 ; and
1%-5% by volume of said source solution of HF.
8. The method recited in claim 7 wherein:
said film forming solution comprises 0.7%±0.5% by volume of said HNO3 source solution.
9. The method recited in claim 5 wherein:
said exposing is for a period of about one minute; and
said treating is for a period of about one minute.
US06/078,795 1979-09-25 1979-09-25 Two step method of cleaning silicon wafers Expired - Lifetime US4261791A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US06/078,795 US4261791A (en) 1979-09-25 1979-09-25 Two step method of cleaning silicon wafers
SE8006355A SE8006355L (en) 1979-09-25 1980-09-11 CLEANING OF SILICONE ISS
IT24611/80A IT1141041B (en) 1979-09-25 1980-09-11 TWO-STAGE METHOD FOR CLEANING SILICON SLABS
DE19803035020 DE3035020A1 (en) 1979-09-25 1980-09-17 METHOD FOR CLEANING A SEMICONDUCTOR DISC
JP13366280A JPS5655053A (en) 1979-09-25 1980-09-24 Method of purifying polluted semiconductor wafer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US06/078,795 US4261791A (en) 1979-09-25 1979-09-25 Two step method of cleaning silicon wafers

Publications (1)

Publication Number Publication Date
US4261791A true US4261791A (en) 1981-04-14

Family

ID=22146275

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/078,795 Expired - Lifetime US4261791A (en) 1979-09-25 1979-09-25 Two step method of cleaning silicon wafers

Country Status (5)

Country Link
US (1) US4261791A (en)
JP (1) JPS5655053A (en)
DE (1) DE3035020A1 (en)
IT (1) IT1141041B (en)
SE (1) SE8006355L (en)

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4615762A (en) * 1985-04-30 1986-10-07 Rca Corporation Method for thinning silicon
US4911783A (en) * 1987-04-15 1990-03-27 Bbc Brown Boveri Ag Process for etching recesses in a silicon substrate
US4964919A (en) * 1988-12-27 1990-10-23 Nalco Chemical Company Cleaning of silicon wafers with an aqueous solution of KOH and a nitrogen-containing compound
EP0437950A2 (en) * 1989-12-20 1991-07-24 Fujitsu Limited Semiconductor device having silicon-on-insulator structure and method of producing the same
EP0477504A1 (en) * 1990-09-26 1992-04-01 International Business Machines Corporation Reduction of foreign particulate matter on semiconductor wafers
EP0548504A2 (en) * 1991-10-29 1993-06-30 HI-SILICON Co., Ltd. Process for cleaning silicon mass
US5250836A (en) * 1989-12-20 1993-10-05 Fujitsu Limited Semiconductor device having silicon-on-insulator structure
US5489557A (en) * 1993-07-30 1996-02-06 Semitool, Inc. Methods for processing semiconductors to reduce surface particles
EP0742583A2 (en) * 1995-05-11 1996-11-13 Wacker Siltronic Gesellschaft für Halbleitermaterialien Aktiengesellschaft Method of removing damaged crystal areas from silicon wafers
US5632866A (en) * 1994-01-12 1997-05-27 Fsi International, Inc. Point-of-use recycling of wafer cleaning substances
US5837662A (en) * 1997-12-12 1998-11-17 Memc Electronic Materials, Inc. Post-lapping cleaning process for silicon wafers
US5972124A (en) * 1998-08-31 1999-10-26 Advanced Micro Devices, Inc. Method for cleaning a surface of a dielectric material
US6004399A (en) * 1996-07-01 1999-12-21 Cypress Semiconductor Corporation Ultra-low particle semiconductor cleaner for removal of particle contamination and residues from surface oxide formation on semiconductor wafers
US6037271A (en) * 1998-10-21 2000-03-14 Fsi International, Inc. Low haze wafer treatment process
US6090726A (en) * 1996-07-05 2000-07-18 National Science Council Pretreatment method of a silicon wafer using nitric acid
US6143663A (en) * 1998-01-22 2000-11-07 Cypress Semiconductor Corporation Employing deionized water and an abrasive surface to polish a semiconductor topography
US6171180B1 (en) 1998-03-31 2001-01-09 Cypress Semiconductor Corporation Planarizing a trench dielectric having an upper surface within a trench spaced below an adjacent polish stop surface
US6200896B1 (en) 1998-01-22 2001-03-13 Cypress Semiconductor Corporation Employing an acidic liquid and an abrasive surface to polish a semiconductor topography
US6232231B1 (en) 1998-08-31 2001-05-15 Cypress Semiconductor Corporation Planarized semiconductor interconnect topography and method for polishing a metal layer to form interconnect
US6240933B1 (en) 1997-05-09 2001-06-05 Semitool, Inc. Methods for cleaning semiconductor surfaces
US6274504B2 (en) * 1999-06-15 2001-08-14 Advanced Micro Devices, Inc. Minimizing metal corrosion during post metal solvent clean
US6526995B1 (en) 1999-06-29 2003-03-04 Intersil Americas Inc. Brushless multipass silicon wafer cleaning process for post chemical mechanical polishing using immersion
US6534378B1 (en) 1998-08-31 2003-03-18 Cypress Semiconductor Corp. Method for forming an integrated circuit device
US6566249B1 (en) 1998-11-09 2003-05-20 Cypress Semiconductor Corp. Planarized semiconductor interconnect topography and method for polishing a metal layer to form wide interconnect structures
US6828678B1 (en) 2002-03-29 2004-12-07 Silicon Magnetic Systems Semiconductor topography with a fill material arranged within a plurality of valleys associated with the surface roughness of the metal layer
US6969684B1 (en) 2001-04-30 2005-11-29 Cypress Semiconductor Corp. Method of making a planarized semiconductor structure
US20070093065A1 (en) * 2005-10-25 2007-04-26 Oki Electric Industry Co., Ltd. Method for manufacturing a semiconductor wafer
US20090007940A1 (en) * 2007-07-04 2009-01-08 Siltronic Ag Process For Cleaning A Semiconductor Wafer Using A Cleaning Solution

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2639008B2 (en) * 1988-10-25 1997-08-06 富士通株式会社 Semiconductor substrate cleaning method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2822250A (en) * 1954-12-01 1958-02-04 Philips Corp Material removal from semi-conductive metal telluride
US3102061A (en) * 1960-01-05 1963-08-27 Texas Instruments Inc Method for thermally etching silicon surfaces
US3224904A (en) * 1963-03-18 1965-12-21 Bell Telephone Labor Inc Semiconductor surface cleaning
US3813311A (en) * 1973-01-24 1974-05-28 Gen Motors Corp Process for etching silicon wafers
US4026741A (en) * 1976-06-16 1977-05-31 Bell Telephone Laboratories, Incorporated Technique for preparation of stoichiometric III-V compound semiconductor surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2822250A (en) * 1954-12-01 1958-02-04 Philips Corp Material removal from semi-conductive metal telluride
US3102061A (en) * 1960-01-05 1963-08-27 Texas Instruments Inc Method for thermally etching silicon surfaces
US3224904A (en) * 1963-03-18 1965-12-21 Bell Telephone Labor Inc Semiconductor surface cleaning
US3813311A (en) * 1973-01-24 1974-05-28 Gen Motors Corp Process for etching silicon wafers
US4026741A (en) * 1976-06-16 1977-05-31 Bell Telephone Laboratories, Incorporated Technique for preparation of stoichiometric III-V compound semiconductor surfaces

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4615762A (en) * 1985-04-30 1986-10-07 Rca Corporation Method for thinning silicon
US4911783A (en) * 1987-04-15 1990-03-27 Bbc Brown Boveri Ag Process for etching recesses in a silicon substrate
US4964919A (en) * 1988-12-27 1990-10-23 Nalco Chemical Company Cleaning of silicon wafers with an aqueous solution of KOH and a nitrogen-containing compound
EP0437950A2 (en) * 1989-12-20 1991-07-24 Fujitsu Limited Semiconductor device having silicon-on-insulator structure and method of producing the same
EP0437950A3 (en) * 1989-12-20 1992-04-22 Fujitsu Limited Semiconductor device having silicon-on-insulator structure and method of producing the same
US5250836A (en) * 1989-12-20 1993-10-05 Fujitsu Limited Semiconductor device having silicon-on-insulator structure
EP0477504A1 (en) * 1990-09-26 1992-04-01 International Business Machines Corporation Reduction of foreign particulate matter on semiconductor wafers
US5294570A (en) * 1990-09-26 1994-03-15 International Business Machines Corporation Reduction of foreign particulate matter on semiconductor wafers
EP0548504B1 (en) * 1991-10-29 1997-01-22 HI-SILICON Co., Ltd. Process for cleaning silicon mass
EP0548504A2 (en) * 1991-10-29 1993-06-30 HI-SILICON Co., Ltd. Process for cleaning silicon mass
US5489557A (en) * 1993-07-30 1996-02-06 Semitool, Inc. Methods for processing semiconductors to reduce surface particles
US5632866A (en) * 1994-01-12 1997-05-27 Fsi International, Inc. Point-of-use recycling of wafer cleaning substances
EP0742583A2 (en) * 1995-05-11 1996-11-13 Wacker Siltronic Gesellschaft für Halbleitermaterialien Aktiengesellschaft Method of removing damaged crystal areas from silicon wafers
EP0742583A3 (en) * 1995-05-11 1997-01-02 Wacker Siltronic Halbleitermat Method of removing damaged crystal areas from silicon wafers
US5911889A (en) * 1995-05-11 1999-06-15 Wacker Siltronic Gesellschaft Fur Halbleitermaterialien Aktiengesellschaft Method of removing damaged crystal regions from silicon wafers
US6004399A (en) * 1996-07-01 1999-12-21 Cypress Semiconductor Corporation Ultra-low particle semiconductor cleaner for removal of particle contamination and residues from surface oxide formation on semiconductor wafers
US6090726A (en) * 1996-07-05 2000-07-18 National Science Council Pretreatment method of a silicon wafer using nitric acid
US6843857B2 (en) 1997-05-09 2005-01-18 Semitool, Inc. Methods for cleaning semiconductor surfaces
US6830628B2 (en) 1997-05-09 2004-12-14 Semitool, Inc. Methods for cleaning semiconductor surfaces
US6240933B1 (en) 1997-05-09 2001-06-05 Semitool, Inc. Methods for cleaning semiconductor surfaces
US20040069320A1 (en) * 1997-05-09 2004-04-15 Semitool, Inc. Methods for cleaning semiconductor surfaces
US5837662A (en) * 1997-12-12 1998-11-17 Memc Electronic Materials, Inc. Post-lapping cleaning process for silicon wafers
US6143663A (en) * 1998-01-22 2000-11-07 Cypress Semiconductor Corporation Employing deionized water and an abrasive surface to polish a semiconductor topography
US6361415B1 (en) 1998-01-22 2002-03-26 Cypress Semiconductor Corp. Employing an acidic liquid and an abrasive surface to polish a semiconductor topography
US6200896B1 (en) 1998-01-22 2001-03-13 Cypress Semiconductor Corporation Employing an acidic liquid and an abrasive surface to polish a semiconductor topography
US6171180B1 (en) 1998-03-31 2001-01-09 Cypress Semiconductor Corporation Planarizing a trench dielectric having an upper surface within a trench spaced below an adjacent polish stop surface
US6849946B2 (en) 1998-08-31 2005-02-01 Cypress Semiconductor Corp. Planarized semiconductor interconnect topography and method for polishing a metal layer to form interconnect
US6302766B1 (en) 1998-08-31 2001-10-16 Cypress Semiconductor Corp. System for cleaning a surface of a dielectric material
US5972124A (en) * 1998-08-31 1999-10-26 Advanced Micro Devices, Inc. Method for cleaning a surface of a dielectric material
US6534378B1 (en) 1998-08-31 2003-03-18 Cypress Semiconductor Corp. Method for forming an integrated circuit device
US6232231B1 (en) 1998-08-31 2001-05-15 Cypress Semiconductor Corporation Planarized semiconductor interconnect topography and method for polishing a metal layer to form interconnect
US6037271A (en) * 1998-10-21 2000-03-14 Fsi International, Inc. Low haze wafer treatment process
US6566249B1 (en) 1998-11-09 2003-05-20 Cypress Semiconductor Corp. Planarized semiconductor interconnect topography and method for polishing a metal layer to form wide interconnect structures
US6274504B2 (en) * 1999-06-15 2001-08-14 Advanced Micro Devices, Inc. Minimizing metal corrosion during post metal solvent clean
US6526995B1 (en) 1999-06-29 2003-03-04 Intersil Americas Inc. Brushless multipass silicon wafer cleaning process for post chemical mechanical polishing using immersion
US6969684B1 (en) 2001-04-30 2005-11-29 Cypress Semiconductor Corp. Method of making a planarized semiconductor structure
US6828678B1 (en) 2002-03-29 2004-12-07 Silicon Magnetic Systems Semiconductor topography with a fill material arranged within a plurality of valleys associated with the surface roughness of the metal layer
US20070093065A1 (en) * 2005-10-25 2007-04-26 Oki Electric Industry Co., Ltd. Method for manufacturing a semiconductor wafer
US20090007940A1 (en) * 2007-07-04 2009-01-08 Siltronic Ag Process For Cleaning A Semiconductor Wafer Using A Cleaning Solution
US7938911B2 (en) * 2007-07-04 2011-05-10 Siltronic Ag Process for cleaning a semiconductor wafer using a cleaning solution

Also Published As

Publication number Publication date
SE8006355L (en) 1981-03-26
IT1141041B (en) 1986-10-01
JPS5655053A (en) 1981-05-15
DE3035020A1 (en) 1981-04-09
IT8024611A0 (en) 1980-09-11

Similar Documents

Publication Publication Date Title
US4261791A (en) Two step method of cleaning silicon wafers
US4116714A (en) Post-polishing semiconductor surface cleaning process
US4050954A (en) Surface treatment of semiconductor substrates
US4129457A (en) Post-polishing cleaning of semiconductor surfaces
US5639311A (en) Method of cleaning brushes used in post CMP semiconductor wafer cleaning operations
KR100597909B1 (en) Methods and Apparatus for Cleaning Semiconductor Substrates after Polishing Copper Film
US5489557A (en) Methods for processing semiconductors to reduce surface particles
KR100220926B1 (en) A cleaning method for hydrophobic silicon wafers
EP1016127B1 (en) A fluorometric method for increasing the efficiency of the rinsing and water recovery process in the manufacture of semiconductor chips
JP3219020B2 (en) Cleaning agent
JPH08187475A (en) Method of removing metal in scrubber
US6100198A (en) Post-planarization, pre-oxide removal ozone treatment
JP2002517090A (en) Alkali treatment after etching
KR100623832B1 (en) Method of reclaiming silicon wafers
JP2643814B2 (en) Semiconductor substrate cleaning method
JP2762230B2 (en) Storage method of silicon wafer
JPH08264498A (en) Silicon wafer cleaning method
KR100433961B1 (en) Aqueous cleaning solution for a semiconductor substrate
KR19980079836A (en) Method of treating a polished semiconductor wafer immediately after polishing the semiconductor wafer
US6451124B1 (en) Process for the chemical treatment of semiconductor wafers
JP2700778B2 (en) Semiconductor material processing method using acid-containing liquid
JP3436696B2 (en) Method and product for preventing edge contamination of silicon wafer by ozone immersion
JPH0750281A (en) Cleaning method for silicon wafer
JP3198878B2 (en) Surface treatment composition and substrate surface treatment method using the same
JPH07321080A (en) Method for cleaning silicon wafer

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE